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Electron tunneling in rhenium-modified Pseudomonas aeruginosa azurins

Miller, Jeremiah E. and Di Bilio, Angel J. and Wehbi, William A. and Green, Michael T. and Museth, A. Katrine and Richards, John R. and Winkler, Jay R. and Gray, Harry B. (2004) Electron tunneling in rhenium-modified Pseudomonas aeruginosa azurins. Biochimica et Biophysica Acta (BBA) - Bioenergetics, 1655 . pp. 59-63. ISSN 0005-2728. doi:10.1016/j.bbabio.2003.06.010.

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Laser flash-quench methods have been used to generate tyrosine and tryptophan radicals in structurally characterized rhenium-modified Pseudomonas aeruginosa azurins. Cu(I) to “Re(II)” electron tunneling in Re(H107) azurin occurs in the microsecond range. This reaction is much faster than that studied previously for Cu(I) to Ru(III) tunneling in Ru(H107) azurin, suggesting that a multistep (“hopping”) mechanism might be involved. Although a Y108 radical can be generated by flash-quenching a Re(H107)M(II) (M=Cu, Zn) protein, the evidence suggests that it is not an active intermediate in the enhanced Cu(I) oxidation. Rather, the likely explanation is rapid conversion of Re(II)(H107) to deprotonated Re(I)(H107 radical), followed by electron tunneling from Cu(I) to the hole in the imidazole ligand.

Item Type:Article
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Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2004 Elsevier B.V. Received 24 April 2003, Revised 26 June 2003, Accepted 26 June 2003, Available online 7 January 2004. Our research on electron tunneling in proteins is supported by NIH grant DK19038.
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Subject Keywords:Electron tunneling; Rhenium complex; Amino acid radical; Blue copper; Azurin
Record Number:CaltechAUTHORS:20170531-085753394
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Official Citation:Jeremiah E. Miller, Angel J. Di Bilio, William A. Wehbi, Michael T. Green, A.Katrine Museth, John R. Richards, Jay R. Winkler, Harry B. Gray, Electron tunneling in rhenium-modified azurins, Biochimica et Biophysica Acta (BBA) - Bioenergetics, Volume 1655, 2004, Pages 59-63, ISSN 0005-2728, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77846
Deposited By: Tony Diaz
Deposited On:31 May 2017 18:49
Last Modified:15 Nov 2021 17:34

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